1、BSI Standards PublicationStationary source emissions Determination of the massconcentration of PCDDs/PCDFsand dioxin-like PCBsPart 4: Sampling and analysis of dioxin-likePCBsBS EN 1948-4:2010+A1:2013BS EN 1948-4:2010+A1:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementa
2、tion of EN 1948-4:2010+A1:2013. It supersedes BS EN 1948-4:2010 which is withdrawn.The start and finish of text introduced or altered by amendment is indicated in the text by tags. Tags indicating changes to CEN text carry the number of the CEN amendment. For example, text altered by CEN amendment A
3、1 is indicated by .The UK participation in its preparation was entrusted by Technical Committee EH/2, Air quality, to Subcommittee EH/2/1, Stationary source emission.A list of organizations represented on this subcommittee can be obtained on request to its secretary.This publication does not purport
4、 to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2014. Published by BSI Standards Limited 2014ISBN 978 0 580 81791 5ICS 13.040.40Compliance with a British Standard cannot confer immunity from legal obligation
5、s.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 April 2012.Amendments/corrigenda issued since publicationDate Text affected28 February 2014 Implementation of CEN amendment A1:2013EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 1948-
6、4:2010+A1 December 2013 ICS 13.040.40 Supersedes EN 1948-4:2010English Version Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs missions de sources fixes - Dtermination de la concentration ma
7、ssique en PCDD/PCDF et PCB de type dioxine - Partie 4: Prlvement et analyse des PCB de type dioxine Emissionen aus stationren Quellen - Bestimmung der Massenkonzentration von PCDD/PCDF und dioxin-hnlichen PCB - Teil 4: Probenahme und Analyse dioxin-hnlicher PCB This European Standard was approved by
8、 CEN on 28 August 2010 and includes Amendment 1 approved by CEN on 23 October 2013. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists an
9、d bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the
10、responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugosla
11、v Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE
12、 NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 1948-4:2010+A1:2013 EEN 1948-4:2010+A1:2013 (E) 2 Contents Page For
13、eword 4 Introduction .5 1 Scope 6 2 Normative references 7 3 Terms and definitions .7 4 Symbols and abbreviations . 10 4.1 General . 10 4.2 Polychlorinated biphenyls . 11 5 Principle of the measurement procedure . 11 6 Device, materials and 13C12-labelled standards . 12 6.1 Device and materials 12 6
14、.2 13C12-labelled standards . 12 7 Safety measures . 13 8 Measurement procedure 13 8.1 Sampling 13 8.2 Extraction 13 8.3 Clean-up . 14 8.4 Final concentration of the sample extracts . 15 8.5 Addition of recovery standards . 15 8.6 Principle of identification and quantification . 15 8.7 Calibration o
15、f the HRGC/HRMS . 16 8.8 Quantification of HRGC/HRMS results . 18 8.8.1 Quantification of the sample . 18 8.8.2 Calculation of the recovery rates of the extraction standards 18 8.8.3 Calculation of the recovery rates of the sampling standards 19 8.9 Calculation of the measurement results 20 8.10 Ana
16、lytical report 20 9 Method validation . 21 9.1 General . 21 9.2 Validation of sampling . 22 9.3 Validation of Analytical Extraction and Clean-up 22 9.3.1 Extraction 22 9.3.2 Clean-up . 22 10 Quality control requirements for the measurement 22 10.1 Use of a validated method . 22 10.2 Use of 13C12-lab
17、elled standards . 23 10.3 Minimum requirements for sampling 23 10.4 Minimum requirements for extraction and clean-up . 24 10.5 Minimum requirements for identification of PCB congeners 24 10.6 Minimum requirements for quantification 25 11 Quality assurance criteria for extraction/clean-up/quantificat
18、ion procedure blanks 26 11.1 Analytical blank. 26 11.2 HRGC/HRMS blank . 26 BS EN 1948-4:2010+A1:2013EN 1948-4:2010+A1:2013 (E) 2 Contents Page Foreword 4 Introduction .5 1 Scope 6 2 Normative references 7 3 Terms and definitions .7 4 Symbols and abbreviations . 10 4.1 General . 10 4.2 Polychlorinat
19、ed biphenyls . 11 5 Principle of the measurement procedure . 11 6 Device, materials and 13C12-labelled standards . 12 6.1 Device and materials 12 6.2 13C12-labelled standards . 12 7 Safety measures . 13 8 Measurement procedure 13 8.1 Sampling 13 8.2 Extraction 13 8.3 Clean-up . 14 8.4 Final concentr
20、ation of the sample extracts . 15 8.5 Addition of recovery standards . 15 8.6 Principle of identification and quantification . 15 8.7 Calibration of the HRGC/HRMS . 16 8.8 Quantification of HRGC/HRMS results . 18 8.8.1 Quantification of the sample . 18 8.8.2 Calculation of the recovery rates of the
21、extraction standards 18 8.8.3 Calculation of the recovery rates of the sampling standards 19 8.9 Calculation of the measurement results 20 8.10 Analytical report 20 9 Method validation . 21 9.1 General . 21 9.2 Validation of sampling . 22 9.3 Validation of Analytical Extraction and Clean-up 22 9.3.1
22、 Extraction 22 9.3.2 Clean-up . 22 10 Quality control requirements for the measurement 22 10.1 Use of a validated method . 22 10.2 Use of 13C12-labelled standards . 23 10.3 Minimum requirements for sampling 23 10.4 Minimum requirements for extraction and clean-up . 24 10.5 Minimum requirements for i
23、dentification of PCB congeners 24 10.6 Minimum requirements for quantification 25 11 Quality assurance criteria for extraction/clean-up/quantification procedure blanks 26 11.1 Analytical blank. 26 11.2 HRGC/HRMS blank . 26 EN 1948-4:2010+A1:2013 (E) 3 12 Performance characteristics 27 12.1 General .
24、 27 12.2 Results of the validation campaign . 27 13 Interferences (informative) . 28 Annex A (informative) Toxicity and toxic equivalency 30 Annex B (informative) Examples of extraction and clean-up procedures 32 B.1 Example for clean-up of PCB and the separation from PCDD/PCDFs . 32 B.1.1 General .
25、 32 B.1.2 Chromatography column I 34 B.1.3 Chromatography column II . 34 B.1.4 Additional clean-up I . 34 B.1.5 Additional clean-up II 35 B.1.5.1 General . 35 B.1.5.2 Carbon Column 35 B.1.5.3 Preparation . 35 B.1.6 Addition of the recovery standard . 35 B.1.7 HRGC/HRMS-analysis . 35 B.2 Description
26、of extraction and clean-up procedures used in the validation campaign 41 Annex C (informative) Evaluation of the performance characteristics . 43 C.1 General . 43 C.2 Interlaboratory comparison study of the analytical method . 43 C.3 Accuracy. 44 C.4 Limits of detection (LOD) and limits of quantific
27、ation (LOQ) . 46 C.5 Recovery. 48 C.6 Breakthrough . 49 Annex D (informative) Recommendations for measuring high concentrations of dioxin-like PCBs 51 Annex E (informative) Possible interferences in dioxin-like PCB analysis 52 Annex F (informative) Measurement of the marker PCBs 28, 52, 101, 138, 15
28、3, and 180 in addition to the 12 dioxin-like PCBs 56 Annex G (informative) Measurement of hexachlorobenzene (HCB) 59 Annex H (informative) Significant technical changes . 60 Annex ZA (informative) Relationship between this European Standard and the essential requirements of EU Directives . 61 Biblio
29、graphy 62 BS EN 1948-4:2010+A1:2013EN 1948-4:2010+A1:2013 (E) 4 Foreword This document (EN 1948-4:2010+A1:2013) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either
30、by publication of an identical text or by endorsement, at the latest by June 2014, and conflicting national standards shall be withdrawn at the latest by June 2014. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELE
31、C shall not be held responsible for identifying any or all such patent rights. This document includes Amendment 1 approved by CEN on 21 October 2013. This document supersedes EN 1948-4:2010. Annex H provides details of significant technical changes between this European Standard and the previous doc
32、ument CEN/TS 1948-4:2007. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and supports essential requirements of EU Directive. For relationship with EU Directive(s), see informative Annex ZA, which is an integral part o
33、f this document. The start and finish of text introduced or altered by amendment is indicated by tags . EN 1948 consists of several parts dealing with the determination of the mass concentration of PCDDs, PCDFs and PCBs in stationary source emissions: Part 1: Sampling of PCDDs/PCDFs Part 2: Extracti
34、on and clean-up of PCDDs/PCDFs Part 3: Identification and quantification of PCDDs/PCDFs Part 4: Sampling and analysis of dioxin-like PCBs The first three parts are necessary for the performance of the PCDD/PCDF measurements. In addition this document EN 1948-4 describes the sampling, extraction and
35、analyses of dioxin-like PCBs and requires references to EN 1948-1, 2, 3. The precision and the performance characteristics of the measurement of PCBs were determined between 2006 and 2008 in a comparison and validation trial at both a waste incinerator and a shredder plant sponsored by the European
36、Commission and the European Free Trade Association. The basic requirements of the determination of PCBs were first published as CEN/TS 1948-4, which served as a basis for these mandated validation measurements. This document EN 1948-4 additionally includes important guidance for sampling and analysi
37、s over a broad concentration range gained during the mandated validation measurements. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech
38、Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.
39、BS EN 1948-4:2010+A1:2013EN 1948-4:2010+A1:2013 (E) 4 Foreword This document (EN 1948-4:2010+A1:2013) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publica
40、tion of an identical text or by endorsement, at the latest by June 2014, and conflicting national standards shall be withdrawn at the latest by June 2014. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall no
41、t be held responsible for identifying any or all such patent rights. This document includes Amendment 1 approved by CEN on 21 October 2013. This document supersedes EN 1948-4:2010. Annex H provides details of significant technical changes between this European Standard and the previous document CEN/
42、TS 1948-4:2007. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and supports essential requirements of EU Directive. For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this doc
43、ument. The start and finish of text introduced or altered by amendment is indicated by tags . EN 1948 consists of several parts dealing with the determination of the mass concentration of PCDDs, PCDFs and PCBs in stationary source emissions: Part 1: Sampling of PCDDs/PCDFs Part 2: Extraction and cle
44、an-up of PCDDs/PCDFs Part 3: Identification and quantification of PCDDs/PCDFs Part 4: Sampling and analysis of dioxin-like PCBs The first three parts are necessary for the performance of the PCDD/PCDF measurements. In addition this document EN 1948-4 describes the sampling, extraction and analyses o
45、f dioxin-like PCBs and requires references to EN 1948-1, 2, 3. The precision and the performance characteristics of the measurement of PCBs were determined between 2006 and 2008 in a comparison and validation trial at both a waste incinerator and a shredder plant sponsored by the European Commission
46、 and the European Free Trade Association. The basic requirements of the determination of PCBs were first published as CEN/TS 1948-4, which served as a basis for these mandated validation measurements. This document EN 1948-4 additionally includes important guidance for sampling and analysis over a b
47、road concentration range gained during the mandated validation measurements. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic,
48、Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. EN 1948-4:
49、2010+A1:2013 (E) 5 Introduction Polychlorinated biphenyls (PCBs) are a group of chlorinated aromatic compounds similar in structure to polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) which consist of 209 individual substances (see Figure 1 for the basic structure). PCBs have been produced intentionally over approximately 50 years until the end of the 1990s with different uses in open and closed systems, e.g. as electrical insulators or dielectric fluids in capacitors and transformers, specialised hydraulic f
